Processes for breaking petroleum emulsions



Patented Feb. 28, 1950 Melvin De Groote, UniversityCity, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrov lite Corporation, Ltd., Wilmington, Del., a corporationof Delaware i Drawing. "Application May 29, 1948, Serial No. 30,187

" --'s c ms; (01252-342) This invention relates to processes or-procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type, and particularly petroleum emul'si'onsfi This application is a continuation-in-part of our copending application Serial No. 666,820, filed May 2, 1946, now abandoned. See our co-pending zligflication Serial No. 8,731,--"filed-- February 1 6,

8 Complementary to the above aspect of our invention is our companion invention concerned with the new chemical products or compounds used as the demulsifying agents in said aforementioned processes or procedures, as well as the application of suchchemical compounds, products, and the like, in various other arts and industries, along with methods for manufacturing said new chemical products, or compounds which are of outstanding value in 'demulsification. .jSe our co-pending application Serial No. 1 0,185, filed May 29, 1948.

' plated may be obtained by oxyethylation of in- 1;; with a polycarboxy acid or anhydride;

. Our invention provides an," economical rapid process for resolving petroleum emulsion? of the water-in-oil type, that are commonly re,- ferred to as "cut oil, roilyoilj? emulsified oil) rally-occurring waters or brines dispersed me. more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion. p It also provides an economical and'rap'id procetc., and which comprise; fine droplets of, n 'atu ess for separating emulsions-"which have been prepared under controlled conditions, from mineral oil, such as crude oil and'frelatiyely soft waters or weak brines. Controlledemulsification and subsequent demulsification' under the conditions just mentioned are of significant value in removing impurities, particularly inorganic salts, frompipelineoil.

Demulsification, as contemplated in the present application, includes the preventive step of commingling the demulsifier with the aqueous component which would or might subsequently become either phase of the emulsion in thefabsence of such precautionary measure. Similarly,

such demulsifier may be mixed with the hydrocarbon component.

Briefly stated, thenewwch'emical "compounds hereinjcontemplated as demulsi-fying agents, are obtained by the oxyethylation of certain f-raotional esters obtained from ricinoleic acid. 81570- same stoichiometrical relationship.

carbons, etc.

1 each structural unit. It is to be noted that this clearly difi'erentiates the herein contemplated compounds from those described in our co-pending application Serial No. 30,188, filed May 29,

Briefly stated, the compounds herein contem (2) Reacting triricinolein with a polycarboxy acid or anhydride and then reacting the ester so obtained with glycerol or glycid so as to introduce two reactive hydroxyl radicals in the terminal carboxylic ester position;

(3) Reacting the polycarboxy acid with glycerol, and then subsequently reacting such product with ricinoleic acid or with triricinolein, diricinolein or monoricinolein; and

(4) 'A combination of the three preceding procedures or other equivalent methods.

- The manufacture of such intermediate products is well known and described in numerous patents and elsewhere in the literature.

Having. obtained. sub-resinous polyesters or other intermediates of the kind described, such products are subjected to "oxyethylation so as to give water-soluble or water-miscible products, and preferably of sufficient solubility to give a clear transparent solution.

' It. has been assumedthat the reaction of a hydroikylated polyester having free carboxylic radicals with a polyethyleneglycol under various conditions, would, in essence, result in a product substantially the same as that obtained by reacting with ethylene oxide, so as to result in the We have found that this is not the case and that the resultant products "are significantly diiierent in composition and are much more effective for a number of purposes, such as, for example, demulsification or petroleum emulsions, break induc'ers in the'doctor treatment of sour hydrothe following formula:

Since this difierence in composition involves the inherent nature of the reactants and re-' sultants, it is deemed desirable to point out clearly the nature of the products herein con-- teinplated when glycerol, ricinoleic acid, or derivatives of glycerol and ricinoleic acid are reacted with polycarbox acids having carbon atoms or less, and particularly dicarboxy acids having 4 to 8 carbon atoms, such as succinic acid, I

It is to :be j noted that none of these acids has more thanli) Previous referencehas been made toour so: f

pending application Serial No. 666,819, filed May 1946, now abandoned. If desired, products of g the kind herein contemplated may be obtained 1 from the triricinolein acidic fractional ester 11 therein described by reacting such acidic fractional ester with glycerol, glycide, or methyl glycide, so as to provide a polyhydroxylated radical which can be subjected to oxyethylation, so as to introduce a plurality of polyglycol radicals, as", distinguished from a, single polyglycol radical? contemplated in our aforementioned co-pending application Serial No. 666,819, filed May 2, 1946,

For

this reason, what is said immediately, r01 lowing is, in essence, a repetition of what issaid in said aforementioned co-pending application in the description of such acidic fractional esters. In said application, the fractional esters are intended for use, without change or addition, for reaction with ethylene oxide, whereas, in the in t ppli i h y ar intended for-use as "some acid, due to the p lyfunctionality of these intermediates, and only after further reaction, a'rethey ready for combination with ethylene oxide.

A preferred intermediatemaybe obtained by est-erification reaction between triricinolein and a 'polybasic carboxylic acid, such'as phthalic acid, followed by treatment with glyoide or the equivalent, Ricinoleic acid may be indicated by on V v onncnmtnonacn onqonc1.0o'on which may be conveniently abbreviated f or many purposes to r HORCOOH gr. HORCQO is the acyloxy grou p oiricinoleic lacid, tririoinolein may be represented by the formula: I

HoRcooom 1 11011000 5 noRooo n.

it, contains the residue of the alcohol glycerol which may. be represented as *caused to react with one mole of triricinolein, an ester product will be obtained according to the following reaction:

HORCOOCH,

coon s O+HORCOO 11- coon CO0RCOO H COOH 5 It is not necessary to use three moles of phthalic anhydride, for example, per mole of triricinolein,

and'if desired, one may use one or two moles,

'- 9 although the preference is to use approximately [2th 2% or 3 moles. In the esterification reaction -'a'bove mentioned, and particularly, if conducted at relatively 1 high temperatures, there may be same molecular rearrangement with the producftion of a compound which may be represented by thc following formula:

ED001100; toocm noocnooc too a noocnooc too H1 materlals. For example, in an esterification reaction between triricinolein and phthalic acid, "the resulting product may comprise more complex molecules, such as the following, which illustrates cross-linkages through the polyhydric alcohol residue;

'Ihooooaootl 10.01:

n 0001200 coon 'iiooocaooc 200110003 H00; JOORCOOCH:

noaoooon COORCOO H:

-OOORCOOOH2 HORCOO H I HOOG ([JOORCOOCH:

It is apparent that other cross-linkages may occur. Such ester products containing. more complex molecules'are also suitable. It is also apparent that there may be great variations in the molecular weight of the product. Thf'e molecular weight of the ester product; as determined by cryoscopic methods, or from obvious composition of the ester, usually runs between about 300 and about 4,000 and is seldom eve'r 6,000. Ester products having a molecular vsie'ight over about 10,000, preferably are not employed. During the esterification reaction there may; be some polymerization and polymerized products, as well as simple monomers may be used. 'Ifhefollowing examples will serve to illustrate the manufacture of raw materials, which can b-converted into intermediates, and then can be subjected to oxyethylation.

TRIRICINOLEIN ACIDIC FRACTIQNAL ESTERS Example 1 reaction can be followed, roughly, withdraw- L ing a small sample of the partially reacted mass and permitting it to cool on a watch crystal. When the reaction has become completed, no crystals of phthalic anhydride appear. When the sample no longer shows the presence of such crystals on cooling, it can be titrated with a standard volumetric alkaline solution, since the acid which remains is due entirely-.Jt'o carboxylic hydrogen in the fractional ester. and not to any unreacted phthalic anhydride. If care is taken not to use too high temperatures which would cause formation of heterocyclicj bodies of the character above referred to, one can depend upon the standard alkaline solution to indicate the disappearance of the phthalic anhydride. not to be inferred, however, that any cyclic bodies, if formed, would be unsuitable.

The product thus obtained, however, seems to consist largely of triricinolein diba'isicphthalates It iS .l a

" of course, by triricinolein monobasic phthalate and triricinolein tribasic phthalite. "This fact is indicated by a molecular weightiieterminaticn and also based on the acid value-which usually runs from a little over 100 to slightly less than 110. Note that comparatively low, temperatures of reaction are employed, so as',,;-, to avoid rearrangement, as previously described.

subjected to oxyethylation.

TRIRICINOLEIN ACIDIC" FRACTIONAL ESTERS Example 2 The same procedure is followed as in the preceding example, without, change, except that maleic anhydride in equimolar amount is substituted for phthalic anhydride so asto give the corresponding maleic acid derivative, 1. e., triricinolein diabasic maleate and triricinolein tribasic maleate.

TRIRICINOLEIN ACIDIC FRACTIONAL ESTERS Example 3 The same procedure is followed win the preceding example, without change, except that adipic acid or anhydride in equimolar amount is substituted for phthalic anhydride so as to give thecorresponding adipic acid derivative, 1. e., triricinolein dibasic adipate and triricinolein tribasic adipate.

TRIRICINOLEIN ACIDIC FRACTIONAL ESTERS- Example 4 TRIRICINOLEIN ACIDIC FRACTIONAL ESTERS I Example 5 The same procedure is followed as in the pre ceding example, without change, except that -di-' glycollic acid in equimolar amount is substituted for phthalic anhydride to give the corresponding diglycollic acid derivative, i. e., triricinolein dibasic diglycollate and triricinolein tribasic diglycollate.

The products of esterification produced according to Examples 1 to 5, are viscous, yellowish or amber-colored, oily or sub-resinous materials resemblin somewhat blown castor oil in consistency, and water-insoluble.

It is to be noted that the triricinolein acidic fractional esters herein contemplated as reactants, are characterized by the fact that they are obtained by esterification reactions involving the use of at least one'mole of the polycarboxy acid per mole of triricinolein. For instance, previous formulae indicate combinations wherein 1 to 3 moles of phthalicanhydride are used per mole of triricinolein. In all instances, regardless of the ratio of polycarboxy reactant to triricinolein, there must be at least one free carboxyl per mole of triricinolein in the finished raw material, which is subjected to further reaction, as described. Such requirement is met,

derived from one mole of triricinolein and one mole of phthalic anhydride. Attention is also directedto the fact that all the, fractional esters are prepared in -such a'mannerthatJthe-finaI product is anhydrous. Having obtained such acidic fractional esters they may be treated immediately with glycide or some equivalent, so as to introduce a dihydric terminai radical. The resultant is an intermediate which can .then be GLYCIDE DERIVATIVE 'OF TRIRICINOLEIN ACIDIC FRACTIQNALv ESTER- Ewample 1 650 pounds of triricinolein acidic fractional ester manufactured as described under the heading of Example 1., preceding. are mixed with one-.

half pound of sodium methylate and then re-" acted with extreme caution with a molecular equivalent of glycide (92 pounds) in three batches of approximately 30' to 3']. pounds each. Such reaction involves extreme precaution and care, for the reason that glycide sometimes reacts with almost'explosivefviolence; A suitable procedure'is as follows: To have the mixture of fractional ester and alkaline catalyst cold, add the glycide. cool to. a temperature of under 15. C. and stir'in'the mass with the. autoclave closed; after the two reactants are thoroughly mixed. the temperature is raised slowly until reaction takes place. As soon as reaction starts, the temperature is controlled. If possible, the temperature should be held at the initial reaction temperature or slightlyabove. Such reactions usually take place below 120 C. In any event, when the reaction is complete, the mass is again allowed to cool and the procedure repeated. The third batch is added in the same manner. Un'' less the reaction takes. place with explosive violence or undue velocity, it is impossible that a temperature of over 140"- C. is reached, and it is exceptional to register any pressure in excess of 100 to 200 pounds. Actually, such reaction may take place without even registering 100 pounds pressure. In any event, however, the reaction with glycide must be handled with extreme care. The product so obtained may be indicated by the following formula: 1

/OH COO.CaHs-OH -COORCOOOH2 CaHsOO JOORCOO E COORCOOCHz 'HORCOO H COORCOO H:

ester, as previously described, andfirst employs an equal molar amount of ethylene oxide (55 pounds) into. approximately equal batches. then this intermediate'product will be free frombar- 8 l boxyllc radicals-,andusually glycide can be employed and a, smoother reaction obtained than in the previous instance. Under such circumstances, the products obtained would be indicated by the following formula:

COORCOOCH2 /H5C:OH4C:OO OOIlEtCQO H -oooc iznoclm p on oooozmoczm 1 on ooonooooirz HORCOOCH -oooRc-oo H:

Such product in either instance can be subjected to oxye'thy'lation so as to introduce two or more polyglycol radicals.

GLYCIDE v DERIVATIVE :OF TRIRICINOLEIN ACIDIC FRACTIONAL ESTER Example 2 foliowin}; formulae:

OH'RCOQCaHs we e ooon

oooaooo 000mm oooaon coon ooonon Previous reference has been made to the fact that triricinolein acidic fractional esters inight be reacted with glycerol as well as with glycide. For example, one mole of triglyceride s-uclia'fs tri ricinolein may be esterified with two niolesrof phthalic anhydride to produce diphthalated" ric- .i' inolein which may be represented by the following formula:

0001100 OOH CaHs-OOCROH If one mole of the diphthalated triricinolein is then esterified with 2 moles of glycerol,- the following product may be obtained:

00012004; oocnmom, 4 7 OaHaOOOROH 000K000 ooocamon) g If 2 moles of diphthalated triricinoleinf armacted with one mole of glycol, for example, a more complex molecule may be formed by cross linkage through the glycol residue, as represented by the following formula: 1

OOCROO O 'C;H5OOCROH OOCROOC OOCROOC- CaHs-OOCROH OOCROOC lent thereof. with a. plurality of polyglycol rad- 7 as follows:

icals. has been previously described:

OOCROO OOCsHKOH):

CgHr-OOCROH were reacted further with two additional moles of glycide, the .result would be that four hydroxyls' would be introduced in the terminal radical ,in'e stead of two,'-as .s hown. Similarly, if such a product were treated with four moles of ethylene oxide and then with four moles of glycide,.each' terminal radical would have four hydroxyl 'radicals available for reaction with ethylene oxide. Thus, it ismanifest that the procedure herein described or some obvious variant thereof, for instance, the use of acyclic diglycerol, or a suitable triglycerol, results in an introduction of a terminal radical having 2, 3 or 4 hydroxylrada icals. By way of illustration, consider the pre: ceding formula and the change that is involved by the treatment of 4 moles of ethylene oxide and then with 4 moles of glycide. The structure of the resulting compound would be substantially oooaooo OOClHt oral-00 12011 OOCROOC. COOCaHs Another procedure suitable for the manufacture ofintermediate products which may be sub-; jected to oxyethylation so as to obtain composi-' tions or compounds of the kind herein contem plated, involves procedures similar to that used in the manufacture of modified polyester;resins, one particular modification involves the use of ricinoleic acid compound only and the products obtained are essentially sub-resinous and viscous liquids rather than solids, but if solid, they-are readily soluble in an'inert solvent. The method ofproducingsuch materials is well known and involves an esterification reaction. The -'reactants employed are generally glycerol, castor oil, or ricinoleic acid, along with the polycarboxy acids, particularly the dicarboxy acids previously described. The esterification reaction may be caused to take place readily upon the application of'heat, the reaction being more rapid the higher the temperature that is employed, but care should be taken not to employ excessively high temperatures, which would cause decomposition. The reaction may, if desired, be

' carried out in the presence of an inert solvent,

such asxylene, which may be removed upon the completion of the reaction. When water is formed as a reaction product, the 'esterification reaction may be conducted under a reflux; con,

If a compound such as the following which 11"v denser, using it is formed. The reaction can also be hastened by passing through the reacting materials a dried inert gas, such asnitrogen or CO2. Generally speaking, however, the" reactions take place rapidly, quickly, and completely, simply by heating substances to enter into the reaction in desired stoichiometric proportions at a temperature above the boiling point of water, usually, between about 110 and 160- C., provided there is no decomposition. The, most desirable products are obtained by compositions in which the ratio of moles of polybasic carb'oxylic acid to moles of hydroxylated partial ester material reacted therewith, is within the ratio of 2 to '1 and 3 tol. Such partial ester may consist of a mixture of diricinolein and monoricinolein. The molecular weight of the ester product, as determined by cryoscopic methods, or" from the obvious com position of the ester product, usually run's'between about 300 and about 4,000 and seldom is over 6,000. It -ma be mentioned that when the polybasic carboxylic acid is used in the an hydride form, esterification can take place-without forming water as a reaction product, unless thesecond carboxyl radical is involved, and that the use of polybasic carboxy acid in anhydride form is normally preferable for this reason.

- During the esterification reaction, there may be some polymerization, especiallyif conditions of esterification are prolonged. This polymeiization is due primarily to formation of more complicated compounds from'monomeric forms, through formation of ester linkage, with loss of water. It is to be understood that reference to ester products of the character herein referred.

to include possible polymerized forms, as well as simple esters or monomers.

The following are specific examples of the preferred intermediate products which can then be subjected to oxyethylation to give the final or ultimate composition.

RESINOUS POLYESTER INTERMEDIA'IE Example 1 Mix 296 pounds of phthalic anhydride with 92 pounds of glycerol, and heat for approximately five to ten minutes'at approximately 125 to a water trap to remove water as 150 C., or longer, until a thin, clear, water-white liquid resin intermediate, containing: no unreacted phthalic anhydride, has: been produced. The resin intermediate isthen mixed with 312 pounds of castor oil and the mixture is: heated to from 150 C. to 250 C; for approximately tenv to thirty minutes, or somewhat longer, if required, to complete reaction, after which it is permitted to cool and is diluted with from;- 10% to 20% ofxylene or other inert solvent;

RESINOUS POLYES'I'ER INTERMEDIATE Example. 2

The same procedure is. followed as inthe preceding example without change, except that maleic anhydride, in equivalent amount substituted for phthalic anhydride so as to give the, corresponding maleic acid. derivative.

RESINOUS POLYESTER INTERMEDIATE Example 3:

for: phthalic anhydride so as to give the QQIIE' sponding adipic acid' derivative.

ceding example, without change, except that suc-' cinic acid in equivalent amount-is substituted for phthalic anhydride so" as to give the corresponding succinic acid derivative.

RESINOUS POLYESTER Examples The same procedure is followed as in the preceding example, without change, except ,that diglycollic acid, in equivalent amount is substituted. for phthalic anhydride so as to give the correspondingldiglycollic acid-derivative.

RESINOUS POLYESTER INTERMEDIATE Example 6 One pound-molepf' monoricinolein is reacted with two pound-molesof phthalic anhydride so as to produce an acidic fractional ester.

RESINOUS POLYESTER INTERMEDIATE Example 7 One pound mole of diricinolein is reacted with two pound moles. of phthalic anhydride so as to produce an acidic fractional ester.

' RESINOUS POLYESTER INTERMEDIATE Example 8 The same procedure-is followed as in- Examples 6 and 7, preceding, except that phthalic anhydride is replaced by variousother preferred dicarboxy reactants in stoichiometrical amounts, such as maleic anhydride, adipic acid, succinic acid, or diglycollic acid.

Although, in light of what has been said previously, there appears to be a wide variety of intermediate products which may be subjected to oxyethylation to yield the composition herein contemplated, yet. casual examination discloses a close relationship between all such intermediates. In each instance, such intermediates are polycarboxy derivatives, particularly dicarboxy derivatives of glyceryl esters of ricinoleic acid al'ong'with additional combined glycerol, if required, to insure. a: structure in which the total valencies of the glyceryl-radical 0r radicals, counting such radical as trivalent, is in excess of the number of ricinoleic acid radicals present, and also characterized by the presence of a reactive hydroxyl radical, other'than the ricinoleyl hydroxyl radical. The following characterization difierentiates such suitable intermediate from those describedin our aforementioned co-pending application Serial No. 666,819, filed May 2, 1946, in that in the present instance, in any particularly monomeric, or structural unit, the number of ricinoleic acid radicals present is less than the number of hydroxyl radicals originally available for esterification, and as a result of this difference,

certain marked difierentiations iii-structure appear, as, for example, the following:

(1) A dicarboxy radical may be directly attached to the residual glyceryl hydroxyl group, such as phthalated monoricinolein or phthalated diricinolein, where the phthalic acid residue is attached'to the glyceryl radical, which is, in essence, attached in a terminal position;

2 Orin an isomer of; the previous type o'f compou d, if thepphthalic acid radical or its equivalent is attached to a ricinolein hydroxyl group, thenand in that event, the residual glyc-- being 130 pounds gauge eryl hydroxyl' is susceptible to' oxyethylationand again provides means for introducing a terminal polyglycol radical; i l r .11

(3) The polyglycol radical introduced in-the ricinoleyl radical, under any circumstances, instead of being a single long chain, may be considered as a branched chain polyglycol radical, or better still, as a plurality of polyglycol radicals having, as desired, from 2 to 4 hydroxyls, ormay have variants in which more than one of these characteristic structures appear.

Generally speaking, oxyethylation is conducted in substantially the same manneras applied to a number of other products, in which the'ethylene oxide group is introduced between an oxygen atom and a hydrogen atom, as, for example, in oxyethylation of high molal acids or high molal alcohols, substituted phenols, etc Usually, a small amount of alkaline catalyst is added, such as one-tenth of 1% to 1% of caustic soda, sodium stearate, sodium methylate, or the like. Oxy- -ethylation is conducted with constant stirring and a gauge pressure of 100 to 200 pounds per square inch is generally satisfactory. The temperature of reaction may be varied from 100'C..to less than 200 C. If desired, an inert solvent may be pres.- ent, such as xylene, tetralin, cymene, decalin or the like. The ethylene oxide maybe used continuously, provided the addition is regulated so that it is used up more or. less uniformly as it enters the reaction vesselor autoclave. 'Our preference, however, is to add the material batchwise, as indicated, and continue oxyethylation not only until the product is distinctly hydrophile, but also until it gives a substantially clear solution in water. As to other oxyethylating procedure, attention is directed to the followingUnited .States patents and to the following British patent: U. S. Nos. 2,142,007, December 27, 1938;72. Schlack; 1,845,198, February 16, 1932, O Schmidt et al.; 1,922,459, August 12, 1933, O. Schmidt et al.; British 302,041, August 7, 1928, J Johnson.

OXYETHYLATED WATER-SOLUBLE DERIVATIVE Example 1 j 550 pounds of a sub-resinous compound exemplified by Resinous polyester intermediate, Example 1 is mixed with one-half; pound of sodium methylate and then reacted with approximately .175 pounds of ethylene oxide in three batches of 55 to 60 pounds each. The maximum'pressure during the reaction is 135 pounds per square inch gauge pressure, along with a temperature of 140 C. The time of react-ion required for each batch varies from 3 to 9 hours. equivalent of the resinous raw material be considered a 1100, then the amount of ethylene If the molecular weight "a suitable permanent solution and is definitely short of the point where a clear solution is produced. For this reason, it is then treated with approximately 200 pounds of additional ethylene oxide, using about 50 pounds per batch. Each one of the four treatments require approximately 10 hours for reaction, the maximum pressure pressure, 'asbeforeha d the temperature somewhat-higher .than in the 14 initial treatment, to wit, to C". The Indterial, at the end of. the. second treatment, is definitely more water-miscible, but gives a very definite cloudy solution which tends to separate. For this reason, further oxyethylation is indicated. This third series of oxyethylations involve the addition of 220 pounds of ethylene oxide in four batches of 55 pounds each. The conditions of reaction are identical with those employed in the batch steps immediatelypreceding. The water-solubility of the derivative-is markedly enhanced. In the last series of oxyethylations there is added 200 pounds of ethylene oxide in 4 portions of 50 pounds each. In the final series of batch treatments less time is required, the ethylene oxide being absorbed in approximately 5 hours, and although the pressure continues in the same range as previously, the temperature employed is somewhat higher, to wit, C. The product obtained is clearly water-soluble and gives an excellent and permanent solution, As

the result of the above procedure, 550 pounds of 'of resin. Figured as an increase in weight, there is added 796 pounds of ethylene oxide to 550 pounds of resin intermediate, or the amountof ethylene oxide added, based on the amount of resin intermediate used as a raw material, represents 144%. The appearance of the product was that of a deep amber-colored, non-viscous oil. The acid value of this product is 1.3. This product is further identified as L-12865.

OXYETHYLATED WATER-SOLUBLE DERIVATIVE Example 2 The same procedure is followed as in the preceding example, except that the amount of ethylene oxide employed is increased by approximately one-sixth, so as to introduce 42 moles of ethylene oxide per mole of resin, in comparison with 36 moles in Example 1, immediately preceding. If

the same amount of resin intermediate is used in the beginning of the reaction, for instance, 550 pounds, then after 795 pounds havebeen added in the manner described in Example 1, immediatel preceding, there is an additional amount added equal to 135 pounds, which is conveniently employed in the form of three batches of 45 pounds each. These additions at this stage can be made with comparative ease, requiring only about 4 hours for each addition at a temperature of 155 C. with a maximum gauge pressure of 130 pounds per inch. At the completion of the reaction, it means that 930 pounds have been added to 550 pounds of intermediate; The ethylene oxide added represents 169%, based on the resin intermediate as a raw material, and this compares with 144%, as in Example 1. Needless to say, the product gives a. clear solution in water and the general appearance is the same as the preceding example.

'OXYETHYLATED WATER-SOLUBLE DERIVATIVE Example 3 i5 wordsfif the product resulting from Example 2, immediately preceding, is considered as a raw material, there is added one morev lot of ethylene oxide equivalent to 135 pounds in 'three batches of 45 pounds each, under the same conditions as described in Example 2, immediately preceding. This brings the ethylene oxide added to 48 moles per mole of resin, compared with36 moles in Example l, preceding, and 42 moles in Example 2, immediately preceding. This represents an addition of 1065 pounds of ethylene oxide to -550 pounds of original resin intermediate. This is equivalent to 193.5% based onthe amount of intermediate used as a raw material. This figure compares with the 144% in Example 1 and 169% in Example 2. The three examples collectively give an excellent guide as to the amount of ethylene oxide to be added to produce the properties herein contemplated in the final compositions. In other words, approximately 140% to 200%, by Weight, of ethylene oxide is added for the purpose f producing suflicient "water solubility in all the various intermediate resins.

OXYETHYLATED WATER-SOLUBLE DERIVATIVE v Example 4 The same procedure is applied to resin intermediates prepared in the manner described under the heading Resinous polyester intermediate, Examples 2 to 7, inclusiveflinstead of the intermediate described under the heading Resinous polyester intermediate,- Example 1, which was employed as a raw material in the manufacture of Oxyethylated water-soluble derivative, Examples 1, 2 and 3, immediately preceding.

OXYETHYLATED WATER-SOLUBLE DERIVATIVE Example 5 The same procedure is applied to glycide derivative triricinolein fractional ester, Examples 1 and 2, instead of the intermediate described under the heading Resinous polyester intermediate,

Example 1; which was employed as a raw mate rial in the manufacture of Oxyethylatecl watersoluble derivative, Examples 1, 2 and 3, immediately preceding. In other words, 550 poundsof "the glycide derivative is used to replace 550 pounds of the Resinous polyester intermediate "Products of value as demulsifyin'g agents have been prepared by reacting acidic products of the kind previously described with .polyhydric alcohols, although not necessarily with polyethylene "glycol's having a large number of repetitious ether linkages in such proportion and manner as to render such products water-soluble or watermiscible.

Esterification of a polyethylene glycol or the like cannot yield the same sort of product as .employed in the manufacture of such products .es have been described, etherization does not take place. More specifically, the conventional condic ew tions of reaction in which a. hydroxylated com pound is treated with a polyethylene glycol, does not yield an ether. For this particular reason, one .would not expect treatment with ethylene oxide to yield the same sort of products as would be, obtained by esterification. For this particular reason, the hereto attached claims are limited to products obtained by the oxyethylation of com.- pounds in which there is present a reactive alcoholic hydroxyl radical, regardless of whether there be present'or absent any free carboxylic radicals. This particularfeature differentiates such products from those obtained by es'terificati'on from polyethylene 'glycols. Furthermore, attention has already been directed to the fact that the intermediates. subjected to oxyethylation contain. ;a

number of ricinoleic'acid radicals which is less than the number of hydroxyl radicals originally available for 'esteri-fication, and thus, is differentiated from our :co-p'ending application Serial No. 666,819, filed May 2, 1946. Attention is also directed to other certain differences in the reactants obtained by treatment with ethylene oxide and esterifl'cation reactions involving a polyethylene glycol Oxyethylation is conducted in absence of water. It is generally conducted at temperatures distinctly under 200 C. In fact, this temperature may be taken as the upper limit; unless a catalyst is added, esterification reactions may require much higher temperatures, vfor instance, i'rom 295 to 335. This difierence may be illustrated by employing any one of the typical "intermediates herein described, for instance,

Resino'us polyester intermediate, Example 1, In other words, if one subjects a. predetermined amount so that the result would be comparable to the products described under the heading "Oxyethylated water-soluble derivative, Example 1., it is possible to make some appraisal of the difference in reaction and resultant, depending upon which of the two procedures is employed. An examination of such .reactions is best conducted on a laboratory scale. In other words, if one starts with approximately 552 grams of the mixture described under the heading Resinous polyester intermediate, Example 1, and having an acid value of approximately 80.6 and a hydroxyl value of approximately 45.3 and adds thereto equivalent of approximately 2 moles of a polyethylene glycol having approximately 10 to 11 structural units, then on completion of the reaction one would anticipate that there would be a drop in acid value to approximately zero, corresponding to the acid value of the product described under the heading Water-soluble derivative, Example 1, along with the elimination of a stoichiometric amount of water, which would be equivalent to 14% grams.

Such reaction can be conducted in any one of three ways: (at) Absence of a catalyst; (b) presence of an acid catalyst; or (0) presence of a basic catalyst. Actually, there'is little or no justification for using a basic catalyst, for the reason that under such circumstances one would not expect to obtain a product comparable to that described under the heading Water-soluble derivative, Example 1; but would expect to get a product in which trans-esterification which is sometimes referred to as ester interchange or alcoholysis would take place. (See Organic Chemistry, Fieser & Fieser, 1944, page 182; and Organic Chemistry, Fuson 8: Snyder, 1942, page 9 2.) I

In conducting these exploratory experiments, itbecom'es obvious that the two points do not soincide, i. e., the production of water of reaction and reduction of the acidity to the value of one or two. In each instance, an attempt was made to carry the reaction to the end point indicated both ways. In the case of the acid catalyst, one-half percent p-toluene sulfonic acid was added. In connection with the polyethylene glycol reactant, attention is directed to the article entitled Technology of the polyethyleneglycols and carbowax compounds, Chemical and Engineering News, volume 23, No. 3, page 247 (1945). Such article points out, among other things, why the value of n as herein contemplated represents an average value rather than specific value, for a single compound. The result of these experiments are indicated by the following table:

viously noted, are within the range which may result in rearrangements. This is particularly true in the presence of catalysts. Furthermore, it is to be noted that the above experiments and the analytical values included are not concerned with a hydroxyethylation of a reactive alcoholic hydroxyl. It will be noted that the herewith appended claims are all concerned with intermediates in which there is present prior to oxyethylation a reactive alcoholic hydroxyl which is part of a polyhydric alcohol radical, as differentiated from a ricinoleyl hydroxyl radical which apparently is not reactive towards ethylene oxide under the circumstances employed.

' The diiference in the nature of the products obtained by the two different procedures is illustrated further by their effect upon emulsions.

Experiment A 11-24145 Experiment B L-24l46 Experiment C L-24l47 Resinous Polyester Intermediate, Example 1.

552 grams Acid v.=80.6.

552 grams Acid v.=80.6.

HO(C HiO).H- 792 grams 792 grams 792 grams.

n=1 or 11 Catalyst. None Toluene Sull'onic Acid- 56% Sodium Mcthylate.

Acid v. of Mixture. 32.2 32.4 30,0,

Conditions to bring acid value Could not get below 10.3..--" Could not get below 16.0."--- Could not got below 6.9.

o 8. out 2.

Time 6 hrs. 6 hrs 6 hrs,

Maximum Temp 335 C 285 0 315 0.

Water eliminated at this point- 100 c. c. (24 c. 0. ml). 160 c. c c. c. (12 c. 0. oil).

Remarks Conditions to bring about elim- Aqunous milky solution Aqueous milky solution Aqueous milky solution.

ination of 14 g. water (theoretical). Time 1% hour 1 hour 3 hours. Maximum Temperatur 295 C 2 5 0 800 C. Acid v.nt this point. 30.! 21.5.. 12.65. Remarks Clear oil; cloudy sol. with Clear oil; cloudy so]. with Clear oll; cloudy sol. with water. water. water.

In comparison with experiments A, B and C, it has been pointed out previously that the resinous polyester intermediate can be treated with ethylene oxide at comparatively low temperature, for instance, 140 C. in absence of water to give a product which is clearly water-soluble and which has an average molecular weight approximately equivalent to that of products obtained in experiments A, B and C, provided there was complete chemical combination. The acid value of the oxyethylated derivative was approximately 2.

In examining experiments A, B, and C, it is to be noted that it was impossible to reduce the acid value in any one of the three cases to that obtainable by oxyethylation, to wit, a value of 2. Actually, the values vary from 12 to 20. Furthermore, the theoretical amount of water which would be expected to be eliminated in experiments A, B and C so as to give a product identical to that previously referred to as Example 1, would be 14 grams of water. Actually, when 14 grams of water had been eliminated in all three cases, the acid value varied from 12 to approximately 33. On the other hand, when the minimum acid value was obtained, even though it did not approach the value of 2, the amount of water eliminated was a great deal more than theory, varying from 40 cc. including 12 cc. of an oil liquid to 160 cc., and in one instance, there was an elimination of 100 cc. of Water along with 24 cc. of oily liquid. Furthermore, in order to obtain the results indicated, instead of using a temperature of approximately 140 C. or somecant fact, and that is that these temperatures employed in experiments A, B and C, as pre- The following table shows results obtained by adding an equal amount of the same four materials to certain emulsions, one emulsifying agent consisting of the product described under the heading Oxyethylated water-soluble derivative, Example 1, and the other three consisting of the clear oils obtained as resultants from experiments A, B and C, described previously in tabular form. Here again it is to be noted that, although the results indicated are concerned with merely one particular derivative, 1. e., phthalic acid derivatives, the results are the same, as far as demulsification when other polycarboxy acid derivatives are examined the same way. This is particularly true of adipic acid, succinic acid, diglycollic acid, etc.

DEMULSIFYING TEST NO. 1

Date of test Oct. 30, 1945 State of California Oil field Oak Canyon Oil company Wickham Lease No. 4 Well No. 4 Percent emulsion in fluid from well 51.0 Percent free water in fluid from Well Trace Percent water obtained by complete demulsification 46 Percent demulsifier in test solution 21 7 Temperature of tests 140 C.

Period of agitation after adding demuls 5 min. Nature of agitation; machine with shaker arm; shakes per min 130 Ratio of demulsifier to well fluid--- 1:6700

L-24145 L-24l46 1,-24147 Ll2865 Blank 111-24145 L-24l46 L-24147 b12865 Blank Time test started, Time test started,

2:45 5 10150. c. 0. water out at c. 0. water out at- 3210 (10/31) 22 16 3 31 Trace 1:25 Trace Trace Trace 10 Trace 5:00 (10/31) 32 31 16 42 Do. Trace Trace Trace 14 Do. 8115 36 35 27 43 D- Trace Trace Trace 16 Do. 8:50 (11/1) 38 37 28 43 Do. 3 3 17 D 9:15 (11/2) 39 as so 43 Do. 3 5 s 19 Do. 9115 11 2 4o 40 32 43 Do. 5 c 4 19 Do. s s 7 20 Do.

It may be desirable to point out that distillable DEMULSIFYING TEST NO. 2 polyglycols of the kind previously referred to and exemplified by nonaethyleneglycol or the like, and t of t t 13, 19 5 particularly those having 8 to 12 oxyalkylated st t f California groups, are sometimes referred to as upper dis Oil field Wflmingtgn tillable ethylene-glycols. (See U. S. Patent No. 011 ompany Royalty service 2,32%,489, dated. July 20, 1943, to De Groote and Lease Sante Fe Keiseli) n 3.2 Although it has been old to subJect emulsions P t emulsion in fluid from to emulsifying agents obtained by reaction be- 11 211 tween certain resinous products and polyhydric P t, free water i fluid from alcohols free from repetitious ether linkages, yet,

n Trace as far as we are aware, products of the kind ext, water t i by cmplified by experiments A, B and C have not plete demulsjfication 1&0 been hereto prepared or employed as demulsify- Percent demulsifier in test solus agentst 2 It is of considerable interest to compare com- Temperature of tests 160 F. pounds of the kind herein described with some- P riod of agitation after adding what analogous compounds described elsewhere demulsifier 5 in the literature or prepared from data appear- Nature of agitation; machine ing elsewhere. The reagents employed, for ex- With shaker arm; shakes per ample, ricinoleic acid, glycerol, ethylene oxide, min 130 phthalic anhydride, etc, can be considered as Rati of demulsifier t n building blocks or structural units which can be fluid 1;5000 fitted together to give various compounds. Castor oil (triricinolein) may be considered as ricinoleic acid and glycerol in combination. Some such other structures may be exemplified L-24145 L-2414e L-21147 Ll2865 Blank by examples which appear in the series of U. S. Patents Nos. 2,295,163 through 2,295,170, inclusive, Time test started, all dated September 8, 1942, to De Groote and 1030 Keiser. Briefly stated, a polyglycol acid ester such 3 Trace d as nonaethyleneglycol dihydrogen dimaleate, or 3 2 dihydrogen diphthalate, obtained by reaction be- 3 4 2 15 Do. tween one mole of nonaethyleneglycol and two 2 g g 58: moles of an appropriate dicarboxy acid or anhy- 7 7 7 16 Do. dride, is reacted with various hydroxylated com- P pounds, including triricinolein, diricinolein, monoricinolein, etc.

The following table briefly describes four such DEMULSIFYING TEST 3 compounds, the first being an ethylene oxide compound of the kind herein specified. In the next Date f 8 13, 1945 three compounds, or products, an ethylene poly- St f Calif r ia Ca f rnia glycol is used instead of ethylene oxide. The Oil fi Wilmington compounds were prepared in an effort to have the Oil compa y Royalty vice ultimate composition of the last three compounds ea Santa e approximate with, or identical to that of the first We compound, in terms of structural units. Percent emulsion in fluid from 60 Needless to say, as has been pointed out already,

well 24.0 such resemblance is only superficial for the rea- Percent free water in fluid from son that, depending on the temperature of reacwell 0.3 tion, order in which reactants are added, and the Percent water obtained by comvery nature of the possible reactions themselves, plete demulsification 22.0 one does obtain products which are inherently Percent demulsifier in test soluand intrinsically different in molecular structure,

tion 2%; size of molecule, etc. Temperature of tests 160 deg. F. It is Well to recall that the use of compounds of Period of agitation after adding demulsifier Nature of agitation; machine with shaker arm; shakes per 5 min.

min 130 Ratio of demulsifier to well fluid 1:5000

even though obscure and difficult to define, acquires a large degree of reality and value in an invention of the kind herein specified even though it is difficult to set forth such qualities in measures which are more concise and specific than those which have been included.

Only a few examples need be repeated at this point to emphasize these differences which, in our opinion, are related to the sizes, shapes, and association of molecules, and especially at interfaces. If phthalated castor oil is reacted with ethylene oxide, one builds up a derivative of the type in which there is always a residual hydroxyl, for the reason that ethylene oxide acts like a monofunctional reactant. If one substitutes a glycol for ethylene oxide, then one is employing a difunctional reactant, and one mole of a glycol can act as a coupling reagent to unite two moles of phthalated castor oil. Likewise, with the glycol and a glyceride, or any ester including a phthalated acid ester, alcoholysis can and usually does take place, particularly at elevated tem-- peratures. This is not true in the case of ethylene oxide.

In examining the above table it will be noted that all radicals shown do not add to quite 100%. The reason is that some connective oxygen atoms are not included, particularly those attached to glycerol and that, in some instances, there may have been elimination of water which affected the final percentage.

Attention is again directed to the fact that 13-24632 typifies a compound of the kind herein described. In b24649 the combination was so prepared that polyethyleneglycol having a molecular weight of 770 was employed to replace the ethylene oxide in an effort to get a somewhat analogous structure. In 11-24648 a polyethyleneglycol having a molecular weight of 1540 was reacted with two moles of phthalic anhydride in a manner comparable to that described in a series of patents previously referred to, to wit, U. S. Patents 2,295,163 through 2,295,170. In 11-24647 the polyglycol having a molecular weight of 1540 was added in a final stage without any attempt to combine previously with phthalic anhydride.

In addition to the four compounds above described, i.e., one derived by the use of ethylene oxide and the others by the use of a polyethyleneglycol, it is obvious that other compounds could be made, including the use of an alkoxy polyethyleneglycol. For instance, one could introduce a residue from a monohydric alcohol, such as methyl alcohol, ethyl alcohol or propyl alcohol, etc., into a glycol. Such alkyl radical is introduced rather easily by simply substituting the monohydric alkyl ester of a glycol for the dihydric glycol. A suitable compound could be obtained I by treating methyl or ethyl alcohol with ethylene oxide so as to give an ether glycol having a single 75 22 hydroxyl and a molecular weight comparable to the molecular weight of the glycol previously described, that is, 7'70 and 1540.

However, removing a terminal hydroxyl radical prevents association and produces all sorts of changes which differentiate derivatives of alkoxy polyethyleneglycols from the corresponding derivatives of the polyethyleneglycols themselves. This is illustrated by noting the comparative wetting efdciencies (which properly in turn are related. to surface activity) in the case of some of the simpler polyglycol fatty acids and a selected alkoxy derivative.

Gonceng'atlon) 5g. per 1 c. c. or Wetting Agent 25 sec. wetting at 25 C.

Methoxy polyethyleneglycol M. W. 550 laurate- 066 Polyethyleneglycol M. W. 1000 dilaurate 140 Polyethyleneglycol M. W. 160 Polyethyleneglycol M. W. 400 dilaurate 220 Polyethyleneglycol M. W. 400 mono-oleate 1. 550 Polyethyleneglycol M. W. 600 mono-oleate 2. 250

As to compounds or mixtures involving the use Per cent of Per cent phthalyl Per cent denti- Per cent Ifyim Ricinoleyl radical in final glycerol 02H) Number Reactants and how made g g producto fg g g radicals 5 1 3 final ll ll: product "g ggz P product --o (0.13.) P

L-24632 Castor oil 1 mole, Glycerine 1 mole, phth. anhyd. 3 moles. 16. 42 16. 42 2. 26 61. 2 Heat the C. O. and glyc. to 260 C. and add the phth.

Add EtO (150 0.). L24649 Phth. anhyd. 0.2 mole plus glycerol 1 mole. Heat at 13.45 13.40 2.5 65.5

150 C. Castor oil lo mole. Heat at 250 C. Polyglycol (M. W. 770). Heat at 200 C. L-24648 Polyglycol 1540 0.1 mole plus phth. anhyd. 0.2 mole plus 13.25 13. 40 2.9 65. 5

glyceryl monoricinoleate 0.1 mole plus glycerine lo mole heated at 240 C. L-24647 Phth. anhyd. 0.2 mole plus glycerol 0.1 mole heated at 13.30 13.2 2.5 65.5

125-150" for 10 min. plus castor oil .033 mole heated at for hr. Polyglycol 1540 0.1 mole heated at a of alkoxy polyethyleneglycol plus castor oil and a dicarboxy acid, see U. S. Patent No. 2,081,266 dated May 25, 1937, to Bruson. Compounds of this type, when compared with L-24633, do not show nearly the comparative effectiveness as ademulsifler, or for other purposes, such as use as a break inducer in the treatment of sour hydrocarbons.

The above compounds were then tested for demulsification on a number of typical emulsions.

Some of the tests are as follows:

DEMULSIFYING TEST NO. 4 Date of test Apr. 2, 1948 State of California Oil field Wilmington Oil company Atlantic Lease #11 Well #11 Per cent emulsion in fluid from well 22 Per cent free water in fluid from well L-24632 L24647 11-24648 L-24649 Per cent Demulsifier l/20,000 1/10,000 1/10 .000 1/l0,000 Blank Time test started, 10:20 0. 0. water out at 1:30 (4/2) 7 4 4 4 Trace. 4:45 4 2 9 5 5 Do. a 12:35 4 2 11 e s 6 Do. 10:45 4/3 11 s s 7 Do. 11:00 4/4 13 7 9 8 Do.

Temperature of tests 90 F. 7 DEMULSITYLNG TEST 5 Period of agitation after adding Date of test Mar. 29, 1948 5 demulsiiier e 5min. State or -l California Nature of agitation; -achine Oil field Signal Hill with shaker arm; shakes per Oil company Shell minute 130 Lease Andrews Ratio of demulsifier to we Well No. 9 fluid -e 120,000

L-24632 D2464? L-24648 L-24649 Per CcntDemulsifier 1 2o,o00 1 2o,ooo 1 20,000 1 2o,o0o Blank Time test started, 11:00 c. 0. water out at- Per cent emulsion in fluid from Well 22 Per cent free water in fiuid from well 8 Per cent Water obtained by complete demulsification 28 Per cent dernulsified in test solution 215% Temperature of tests 90 F. Period of agitation after adding dernulsifier 3 min.

' Nature of agitation; machine with shaker arm; shakes per minute 130 In addition to the foregoing demulsifying tests, the same four compounds identified as L-24632, 11-24647, b24648 and 11-24649, have been tested on other emulsions with comparable (inferences. For sake of brevity these other tests are omitted but they include, among others, a test on an oil from the Wood Lease Well No. 2, Stanolind Oil and Gas Company, South Houston Field, located near Houston, Texas, a number of wells located on the properties of the Texas Company at West Columbia, Texas, etc.

These series of tests reveal that the compound obtained by the use of ethylene oxide was to better in numerous instances, and not Ratio of demulsifier to well fiuid 1 :20,000 infrequently was better.

Percent Demulsifier 1/20,000 1/20,000 l/20,000 1/20,000 Blank Time test started, 10:40 0. 0. Water out at (3/29) 7 2 2 3 Trace;

8/15 (3 30 14 7 e 8 Do.

5:00 3/30 r 15 9 9 10 Do.

9:00 3/31 2s 11 11 11 Do.

DEMULSIFYING TEST NO. 6 What has been said previously in regard to the Date of test Man 29, 1948 structure of compounds which appear to be anstate of California alogous at first superficial examination, should on fi ld Kettleman Hills be reconsidered in light of the previous descrip- Oil company KNDA 5 tion of b24632, 11-24547, 13-24648 and L24649, Lease together with the foregoing tests. The same sorts W811 54 of difierences would be shown in other comcent emulsion in fluid from parable tests where surface activity is concerned 11 72 with the industrial application, as for instance, p cent free Water in fluid from '70 break induction in doctor treatment of sour hywell 4 dIO ELI OIIS. The fact that there is a similarity, Per t water Obtained by in fact, almost an identity of structure, when complete demulsification so measured in terms of acid radicals, ethylene oxide Per cent demulsifier in test s luradicals, etc., does not mean that the size of moltion 2.5% 75 ecules is the same for the obvious reason that the 25 same materials of construction yield architecturally different products.

Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water; petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur-dioxide extract, obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of our process may be admixed with one or more of the solvents, customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone, or in admixture with other suitable wellknown classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form which exhibits both oil and water solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are sometimes used in a ratio of l to 10,000, or 1 to 20 000, or even 1 to 30,000, or even 1 to 40,000, or 1 to 50 000, in desalting practice, such as apparent insolubility in oil and water, is not significant, because said reagents undoubtedly have solubility within the concentration employed. This same fact is true in regard to the material or materials employed as the demulsifying agent of our process.

We desire to point out that the superiority of the reagent or demulsifying agent contemplated in our process is based upon its ability to treat certain emulsions more advantageously and at somewhat lower cost than is possible with other available demulsifiers, or conventional mixtures thereof. It is believed that the particular demulsifying a ent or treat ng agent herein described will find comparatively limited application, so far as the majority of oil field emulsions are concerned; but we have found that such a demulsifying agent has commercial value, as it will economically break or resolve oil field emulsions in a number of cases which cannot be treated as easily or at so low a cost with the demulsifying agents heretofore available.

In practising our process for resolving petroleum emulsions of the water-in-oil type, a treating agent or demulsifying agent of the kind above described is brought into contact with or caused to act upon the emulsion to be treated in any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used either alone or in combination with other demulsifying procedure, such as the electrical dehydration process.

The demulsifier herein contemplated may be employed in connection with what is commonly known as down-the-hole procedure, i. e., bringing the demulsifier in contact with the fluids of the well at the bottom of the well, or at some point prior to the emergency of said fluids. This particular type of application is decidedly feasible when the demulsifier is used in connection with acidification of calcareous oil-bearing strata, es-' pecially if suspended in or dissolved in the acid employed for acidification.

7 undue dimculties.

A somewhat analogous use of our demulsifying agent is the removal of a residual mud sheath 1 which remains after drilling a well by the rotary method. Sometimes the drilling mud contains added calcium carbonate or the like to render the mud susceptible to reaction with hydrochloric 4 acid or the like, and thus expedite its removal.

One preferred and more narrow aspect of our invention, insofar as it is concerned with demulsification of petroleum emulsions of theto the mixture if more than one solvent is employed, and generally speaking, it is our preference to employ the demulsifier in a form repre-' senting 25% to 85% demulsifier and 15% to 75% solvent, largely, if not entirely, non-aqueous and so selected as to give a solution or mixture particularly adaptable for proportional pumps or, The following exam ples will illustrate this aspect of our invention.

other measuring devices.

DEMULSIFIER Example 1 Per cent Oxyethylated water-soluble derivative,

Example 1 Xylene 20- Isopropyl alcohol 20 DEMULSIFIER Example 2 Per cent Oxyethylated water-soluble derivative,

Example 4 70 Cresylic d 20 Normal butyl alcohol 10 DEMULSIFIER.

Example 3 Per cent Oxyethylated water-soluble derivative,

Example 4 '70 Aromatic petroleum solvent 10 Isobutyl alcohol 10 Acetone 10 DEMULSIFIER Example 4 Per cent I Oxyethylated water-soluble derivative,

Example 4 Methyl alcohol 15 Dichloroethylether 20 DEMULSIFIER Example 5 Per cent Oxyethylated water-soluble derivative,

Example 5 77% Denatured alcohol 12 Phenol 10 period of time, or for such extended period of.

time as would unquestionably permit its utiliza tion for the herein designated purposes without Attention is directed to th fact that, although it is specified that the intermediates herein contemplated for reaction with ethylene oxide must have a reactive hydroxyl radical, as differentiated from a hydroxyl radical which is part of the ricinoleyl radical, it is to be emphasized that there may also be present a free carboxyl radical. This is exemplified by compounds such as diric inolein monophthalate, diricinolein, diphthalate, monoricinolein monophthalate, monoricinolein diphthalate, or similar compounds derived from other dicarboxy or tricarboxy acids. Naturally, such carboxyl radical is converted in the early stages of oxyethylation into a terminal radical having reactive hydroxyl radicals, i. e., capable of further reaction with ethylene oxide. The acid value of the reactant subjected to oxyethylation may vary from zero, in the case of the glycide derivatives of triricinolein acidic fractional ester, reviously described, to values of 168 or somewhat higher. The latter value happens to be the acid value for monoricinolein diphthalate. Naturally, this value would increase if a dicarboxy acid of lower molecular weight than phthalic acid were employed, and would also increase markedly if a tricarboxy acid such as citric acid were employed, as, for example, in the case of monoricinolein dicitrate formed by the reaction of one citric acid carboxyl only.

The hydroxyl values of the reactants prior to oxyethylation may vary Widely, as is obvious by consideration of some of the formulae or suggested examples. In the case of monoricinolein monophthalate, the value would be 216, whereas, in numerous other compounds illustrated, the value would be as low as 25. The value for resinous polyester intermediate Example 1, de scribed previously, is approximately 40. The acid value, it is noted in that particular instance. is 80.

The preferred ultimate materials are those exemplified by Oxyethylated water-soluble derivatives, Examples 1, 2 and 3. These are obtained, in turn, from resinous polyester interrrrd ates, Examples 1 to 8, inclusive. The preferred type of reactant, prior to oxyethylation, will show a hydroxyl value varying from 25 to 100 and an acid value from 40 to 125. The acid value of the final product is, of course, zero, or substantially zero, for the reasons previously stated, to wit, that all carboxy radicals are converted into hydroxyl radicals. The hydroxyl value of the final product can be calculated by adding the acid value to the hydroxyl value of the reactant prior to oxyethylation and then allowing for increase in weight, due to oxyethylation. Thus, in the case of an intermediate having an acid Value of approximately 80 and a hydroxyl value of approximately 40, and if the amount of ethylene oxide added is suflicient to double the weight of the original reactant, then the final hydroxyl value will be approximately 60 and the acid value will be approximately zero.

The products herein described, and employed as demulsifying agents in our process, may be considered as intermediates for further reaction. For example, they maybe reacted with chloroacetic acid or similar low molal alpha-helm genated carboxy acid to produce an ester. Such ester will serve many of the purposes herein described, i. e., as a demulsifier, break inducer, etc. Such alpha-halogenated carboxy acid ester may be reacted further, for example, with a tertiary amine, such as dimethyldodecylamine, esterified triethanolamlne, in which the acyl radical is derived from a detergent-forming monocarboxy acid, and from hydroxylated amines, obtained, ior example, by reaction with high molal amines, such as octadecylamine with two moles of ethylene oxide. Such compounds or derivatives again can be employed for all of the various purposes herein indicated, and particularly for demulsification.

The word miscible is frequently used to mean soluble in all proportions. In a technical sense, it is sometimes employed to mean soluble, without necessarily meaning in all proportions, and such solubility may include a colloidal dispersion or sol, as well as molecular solution. The word water-miscible is employed in the hereto appended claims in this more restricted meaning.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

1. A process for breaking petroleum emulsions of the Water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier including a water miscible oxyethylated ricinoleic acid-polycarboxy acid-glycerol ester; said ricinoleic acid ester containng at least one glyceryl radial as an integral part thereof and being the ester of a saturated polycarboxy acid having not over 10 carbon atoms; said ester being additionally charaeterized by the fact that (a) The total number or" ricinoleic acid radicals is less than the hypothetical number of hydroxyl radicals orig'nally in combination with a glyceryl radical; and (b) The presence of a reactive hydroxyl radical; said hydroxyl radical being reactive towards ethylene oxide, as differentiated from a ricinoleyl hydroxyl radical, and with the further proviso that the weight of ethylene oxide added by reaction based on the weight of said ricinoleic acid-polycarboxy acid-glycerol ester is within the range of 140% to 200%.

2. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier including a water-mscible oxyethylated ricinoleic acid-dicarboxy acid-glycerol ester; said ricinoleic acid ester containing at least one glyceryl radical as an integral part thereof and being the ester of a saturated dicarboxy acid having not over 10 carbon atoms; said ester being additionally characterized by the fact that (a) The total number of ricinoleic acid radicals is less than the hypothetical number of hydroxyl rad.- icals originally in combination with a glyceryl radical; and (b) The presence of a reactive hydroxyl radical; said hydroxyl radical being reactive towards ethylene oxide, as differentiated from a ricinoleyl hydroxyl radical, and with the further proviso that the Weight of ethylene oxide added by reaction based on the weight of said ricinoleic acid-dicarboxy acid-glycerol ester is within the range of 140% to 200%.

3.- A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action. of a demulsifier includ ng a water-miscible oxyethylated ricinoleic acid-dicarboxy add-glycerol ester; said ricinoleic acid ester containing at least one glyceryl radical as an integral part thereof and being the ester of a saturated dicarboxy acid having at least l, and not more than 8 carbon atoms; said ester being additionally characterized by the fact that (a) The total number of ricinoleic acid radicals is less than the hypothetical number of hydroxyl radicals originally in combination with a glyceryl radical; and (b) The presence of a reactive hydroxyl radical; said hydroxyl radical being reactive towards ethylene oxide, as differentiated from a ricinoleyl hydroxyl radical, and with the further proviso that the weight of ethylene oxide added by reaction based on the weight of said ricinoleic acid-dicarboxy acidglycerol ester is within the range of 140% to 200%.

4. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier including a water-miscible oxyethylated ricinoleic acid-dicarboxy ac d-glycerol ester; said ricinoleic acid ester containing at least one glyceryl radical as an integral part thereof and being the ester of a saturated dicarboxy acid having at least 4 and not more than 8 carbon atoms; said ester being additionally characterized by the fact that (a) The total number of ricinoleic acid radicals is less than the hypothetical number of hydroxyl radicals originally in combination with a glyceryl radical; and (b) The presence of a re-- active hydroxyl radical; said hydroxyl radical being reactive towards ethylene oxide, as differentiated from a ricinoleyl hydroxyl radical; and with the additional proviso that said ricinoleic acid-dicarboxy acid-glycerol ester shall have an acid value within the limits of 40 to 125, and with the further proviso that the weight of ethylene oxide added by reaction based on the weight of said ricinoleic acid-dicarboxy acid-glycerol ester is within the range of 140% to 200%.

5. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier including a water-miscible oxyethylated ricinoleic acid-dicarboxy acid-glycerol ester; said ricinoleic acid ester containing at least one glyceryl radical as an integral part thereof and being the ester of a saturated dicarboxy acid having at least 4 and not more than 8 carbon atoms; said ester being additionally characterized by the fact that (a) The total number of ricinoleic acid radicals is less than the hypothetical number of hydroxyl radicals originally in combination with a glyceryl radical; and (b) The presence of a reactive hydroxyl radical; said hydroxyl radical being reactive towards ethylene oxide, as differentiated from a ricinoleyl hydroxyl radical; and with the additional proviso that said ricinoleic acid-dicarboxy acid-glycerol ester shall have an acid value within the limits of 40 to 125, a hydroxyl value within the limits of 25 to 100; and the weight of ethylene oxide added by reaction based on the weight of said ricinoleic acid-dicarboxy acid-glycerol ester prior to oxyethylation is within the range of 140% to 200%.

6. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier including a water-miscible oxyethylated ricinoleic acid-phthalic acid glycerol ester; said ricinoleic acid ester containing at least one glyceryl radical as an integral part thereof and being the phthalic acid ester; said ester being additionally characterized by the fact that (a) The total number of ricinoleic acid radicals is less than the hypothetical number of hydroxyl radicals originally in combination with a glyceryl radical; and (b) The presence of a reactive hydroxyl radical; said hydroxyl radical being reactive towards ethylene oxide, as differentiated from a ricinoleyl hydroxyl radical; and with the additional proviso that said ricinoleic acid-phthalic acid-glycerol ester shall have an acid value within the limits of to 125, a hydroxyl value within the limits of 25 to 100; and the weight of ethylene oxide added by reaction based on the weight of said ricinoleic acidphthalic acid-glycerol ester prior to oxyethylation is within the range of 140% to 200%.

7. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier including a water-miscible oxyethylated ricinoleic acid-diglycollic acid-glycerol ester; said ricinoleic acid ester containing at least one glyceryl radical as an integral part thereof and being the diglycollic acid ester; said ester being additionally characterized by the fact that (a) The total number of ricinoleic acid radicals is less than the hypothetical number of hydroxyl radicals originally in combination with a glyceryl radical; and (b) The presence of a reactive hydroxyl radical; said hydroxyl radical being reactive towards ethylene oxide, as differentiated from a ricinoleyl hydroxyl radical; and with the additional proviso that said ricinoleic acid-diglycollic acid-glycerol ester shall have an acid value within the limits of 40 to 125, a hydroxyl value within the limits of 25 to and the weight of ethylene oxide added by reaction based on the weight of said ricinoleic acid-diglycollic acid-glycerol ester prior to oxyethylation is within the range of to 200%. 8. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subj ecting the emulsion to the action of a demulsifler including a water-miscible oxyethylated ricinoleic acid-adipie acid-glycerol ester; said ricinoleic acid ester containing at least one glyceryl radical as an integral part thereof and being the adipic acid ester; said ester being additionally characterized by the fact that (a) The total number of ricinoleic acid radicals is less than the hypothetical number of hydroxyl radicals originally in combination with a glyceryl radical; and (b) The presence of a reactive hydroxyl radical; said hydroxyl radical being reactiv towards ethylene oxide, as diiferentiated from a ricinoleyl hydroxy. radical; and with the additional proviso that said ricinoleic acid-adipic acid-glycerol ester shall have an acid value within the limits of 40 to 125, a hydroxyl value within the limits of 25 to 100; and the weight of ethylene oxide added by reaction based cn the weight of said ricinoleic acid-adipic acid-glycerol ester prior to oxyethylation is within the range of 140% to 200%.

MELVIN DE GROOTE. BERNHARD KEISER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,281,419 De Groote et al. Apr. 28, 1942 2,295,163 De Groote et al. Sept. 8, 1942 2,295,168 De Groote et a1. Sept. 8, 1942 2,295,169 De Groote et a1. Sept. 8, 1942 2,307,058 Moeller Jan. 5, 1943 2,353,695 De Groote et a1. July 18, 1944 2,353,701 De Groote et al. July 18, 1944 2,423,364 Blair et a1. July 1, 1947 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE, CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION TO A DEMULSIFIER INCLUDING A WATER-MISCIBLE OXYETHYLATED RICINOLEIC ACID-POLYCARBOCY ACID-GLYCEROL ESTER; SAID RICINOLEIC ACID ESTER CONTAINING AT LEAST ONE GLYCERYL RADIAL AS AN INTEGRAL PART THEREOF AND BEING THE ESTER OF A SATURATED POLYCARBOXY ACID HAVING NOT OVER 10 CARBON ATOMS; SAID ESTER BEING ADDITIONALLY CHARACTERIZED BY THE FACT THAT (A) THE TOTAL NUMBER OF RICINOLEIC ACID RADICALS IS LESS THAN THE HYPOTHETICAL NUMBER OF HYDROXYL RADICALS ORIGINALLY IN COMBINATION WITH A GLYCERYL RADICAL; AND (B) THE PRESENCE OF A REACTIVE HYDROXYL RADICAL; SAID HYDROXYL RADICAL BEING REACTIVE TOWARDS ETHYLENE OXIDE, AS DIFFERENTIATED FROM A RICIOLEYL HYDROXYL RADICAL, AND WITH THE FURTHER PROVISO THAT THE WEIGHT OF ETHYLENE OXIDE ADDED BY REACTION BASED ON THE WEIGHT OF SAID RICINOLEIC ACID-POLYCARBOXY ACID-GLYCEROL ESTER IS WITHIN THE RANGE OF 140% TO 200%. 